CN1959997B - Photoconductive layer forming radiation image taking panel and radiation image taking panel - Google Patents
Photoconductive layer forming radiation image taking panel and radiation image taking panel Download PDFInfo
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- CN1959997B CN1959997B CN2006101432525A CN200610143252A CN1959997B CN 1959997 B CN1959997 B CN 1959997B CN 2006101432525 A CN2006101432525 A CN 2006101432525A CN 200610143252 A CN200610143252 A CN 200610143252A CN 1959997 B CN1959997 B CN 1959997B
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- photoconductive layer
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- image taking
- selenium
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- 230000005855 radiation Effects 0.000 title claims abstract description 51
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- 229910001370 Se alloy Inorganic materials 0.000 claims abstract description 67
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 239000011669 selenium Substances 0.000 claims description 81
- 229910052798 chalcogen Inorganic materials 0.000 claims description 28
- 150000001787 chalcogens Chemical class 0.000 claims description 28
- 229910000528 Na alloy Inorganic materials 0.000 claims description 5
- 229910000967 As alloy Inorganic materials 0.000 claims description 4
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 3
- 150000004770 chalcogenides Chemical class 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 103
- 230000002285 radioactive effect Effects 0.000 description 57
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- 239000010408 film Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 22
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- 238000006243 chemical reaction Methods 0.000 description 9
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- 238000004458 analytical method Methods 0.000 description 8
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- 238000002360 preparation method Methods 0.000 description 5
- 229940007424 antimony trisulfide Drugs 0.000 description 4
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910052716 thallium Inorganic materials 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
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- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910001215 Te alloy Inorganic materials 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 150000001340 alkali metals Chemical class 0.000 description 2
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- 229910000420 cerium oxide Inorganic materials 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018110 Se—Te Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000953555 Theama Species 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000005260 alpha ray Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- LBAIJNRSTQHDMR-UHFFFAOYSA-N magnesium phthalocyanine Chemical compound [Mg].C12=CC=CC=C2C(N=C2NC(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2N1 LBAIJNRSTQHDMR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/08—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic
- G03G5/082—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being inorganic and not being incorporated in a bonding material, e.g. vacuum deposited
- G03G5/08207—Selenium-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14665—Imagers using a photoconductor layer
- H01L27/14676—X-ray, gamma-ray or corpuscular radiation imagers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0272—Selenium or tellurium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0272—Selenium or tellurium
- H01L31/02725—Selenium or tellurium characterised by the doping material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/085—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors the device being sensitive to very short wavelength, e.g. X-ray, Gamma-rays
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Electromagnetism (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Measurement Of Radiation (AREA)
- Solid State Image Pick-Up Elements (AREA)
Abstract
A photoconductive layer for a radiation image taking panel is formed by selenium alloy containing 0.1 to 1000 molar ppm of monovalent metal and 0.1 to 1000 molar ppm of a chalcogenide element other than Se or selenium alloy containing 0.1 to 1000 molar ppm of monovalent metal and 0.1 to 4000 molar ppm of a V group element.
Description
Technical field
The present invention relates to a kind of radiation image taking panel (radiation image taking panel) that is fit to X-ray camera system such as x-ray system for example, more particularly, the present invention relates to form the photoconductive layer (also being " photoconductive layer ") of radiation image taking panel.
Background technology
Known a kind of radioscopic image taking panel, wherein in order to reduce the dose radiation that tested person person is exposed in medical x-ray bombardment, use photoconductive layer to the X ray sensitivity as photosensitive body with use up perhaps that multi-electrode reads and be recorded in the electrostatic latent image that forms with X ray on the photoconductive layer.Because this program has high resolution, so compare with the conventional emission (indirect shooting) indirectly that utilizes the TV camera tube, this program is excellent.
The radioscopic image taking panel, the projection of response X ray on the charge generation layer of configuration therein produces the electric charge corresponding to the energy of X ray, read the electric charge of generation as the signal of telecommunication, thereby this photoconductive layer plays charge generation layer.Normally, amorphous selenium (a-Se), PbO, PbI
2, HgI
2, BiI
3, Cd (ZN) Te etc. is as the material of photoconductive layer.
Although prepare amorphous selenium easily in large area with film techniques such as for example vacuum moulding machines, this amorphous selenium will comprise many amorphous intrinsic faults of construction, the easy variation of sensitivity.Therefore, impurity is widely used, and for example discloses in the 2003-315464 communique in Japanese unexamined patent, discloses a kind of photoconductive layer that uses the amorphous selenium of alkali doped.
In addition, known purpose, added for example chalcogen (" Photographic Science and Engineering " Vol.26, p245,1982) such as Te for spread spectrum sensitivity band.Although can suppress the sensitivity variation, it is reported, " Photographic Science and Engineering " Vol.26, p245, the after image characteristic of the photoconduction of disclosed photoconductive layer is not enough in 1982.
In addition, also know, for example add V group elements such as As in order to stop crystallization or to improve electron transfer.(“Journal?of?Vacuum?Science?and?Technology”Vol.9，pp.387-390，1972)。In addition, in open 2001-284628 number of Japanese unexamined patent the impurity in the selenium is disclosed.
Because in the amorphous selenium of alkali doped, it is disclosed that for example Japanese unexamined patent discloses the 2003-315464 communique, take place local-crystalized, when in photoconductive layer, using the amorphous selenium of alkali doped, because the image deflects that cause time lapse take place easily.
Summary of the invention
Based on above-mentioned observation and explanation, main purpose of the present invention provides a kind of photoconductive layer and is equipped with the radiation image taking panel of this photoconductive layer, and the after image characteristic that the sensitivity variation of described photoconductive layer gets still less with photoconduction is improved.
Another object of the present invention provides the photoconductive layer that a kind of crystallisation problems is overcome and is equipped with the radiation image taking panel of this photoconductive layer, the electron transition of described photoconductive layer be modified and since the image deflects of time lapse be suppressed.
Can realize the preceding purpose of planting of the present invention with first photoconductive layer that forms the radiation image taking panel, be characterised in that it is formed by the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se.
" monovalent metal " is meant alkali metal (Li, Na, K, Rb, Cs), Tl, Ag, Cu etc., and " chalcogen except that Se " is meant S or Te.
Preferred monovalent metal is the Na that Na and selenium alloy contain 0.2～200 molar ppm.Preferred chalcogen is the Te that Te and selenium alloy contain 0.1～400 molar ppm.
According to the present invention, a kind of first radiation image taking panel is provided, it is characterized in that it comprises first photoconductive layer that forms with selenium alloy, described selenium alloy contains 0.1～1000 molar ppm monovalent metal and the chalcogen (chalcogenide element) of 0.1～1000 molar ppm except that Se.
The content of monovalent metal is than raw materials used low about double figures in the photoconductive layer, and the content of chalcogen is than raw materials used low about 20% to one digit number in the photoconductive layer, and this is because due to its distillation effect when being about 1000 molar ppm.Therefore, in Product Status, photoconductive layer of the present invention comprises the selenium alloy that wherein contains 0.001～10 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se.
Can realize back of the present invention kind purpose with second photoconductive layer that forms the radiation image taking panel, it is characterized in that it comprises the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and 0.1～4000 molar ppm V group element.
" monovalent metal " is meant alkali metal (Li, Na, K, Rb, Cs), Tl, Ag, Cu etc., and " V group element " is meant N, P, As, Sb or Bi." selenium alloy " is meant the alloy of selenium and one or more elements except that selenium.
Preferred monovalent metal is the Na that Na and selenium alloy contain 0.2～300 molar ppm.Preferred V group element is the Sb that Sb and selenium alloy contain 0.15～20 molar ppm.In addition, preferred V group element is the As that As and selenium alloy contain 1.5～4000 molar ppm.
According to the present invention, a kind of second radiation image taking panel is provided, it is characterized in that it comprises second photoconductive layer that forms with selenium alloy, described selenium alloy contains the V group element of 0.1～1000 molar ppm monovalent metal and 0.1～4000 molar ppm.
The content of monovalent metal is than raw materials used low about double figures in the product, and in the product V group element content than raw materials used low pact half to one digit number, this is because due to its distillation effect when being about 1000 molar ppm.Therefore, in Product Status, photoconductive layer of the present invention comprises the selenium alloy that wherein contains 0.001～10 molar ppm monovalent metal and the V group element of 0.1～2000 molar ppm except that Se.
Because first photoconductive layer of the present invention comprises the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se, so its sensitivity variation gets still less, the rate of decay of X ray photoelectric current is improved, thereby can shorten the time interval that forms image, increase output.Therefore, first photoconductive layer of the present invention has the after image characteristic of excellent animation and better photoconduction.
Especially, when monovalent metal be Na and selenium alloy to contain 0.2～200 molar ppm Na and chalcogen be Te and selenium alloy when containing the Te of 0.1～400 molar ppm, first photoconductive layer has the after image characteristic of better photoconduction.
In second photoconductive layer of the present invention, local-crystalized more difficult generation, thus electron transition is improved, and the increase that responds the image deflects of local-crystalized development in time is inhibited.
Especially, when monovalent metal be Na and selenium alloy contain 0.2～300 molar ppm Na and V group element be Sb and selenium alloy to contain 0.15～20 molar ppm Sb or V group element be As and selenium alloy when containing 1.5～4000 molar ppm As, the increase that responds the image deflects of local-crystalized development in time is inhibited.
Description of drawings
Fig. 1 is the profile of an example of the expression radiation image taking panel that uses photoconductive layer of the present invention.
Fig. 2 is the schematic diagram that the record/reading system of radiation image taking panel is used in expression.
Fig. 3 A～3D is the figure that the sub-image of expression charge model forms program.
Fig. 4 A～4D is the figure of expression with the sub-image fetch program of the record/reading system of charge model.
Fig. 5 is the schematic diagram of expression radio-active ray sensor with the state of AMA plate integration.
Fig. 6 is the circuit diagram of the equivalent electric circuit of expression AMA plate.
Fig. 7 is the constructed profile of the pixel of expression radioactive ray test section.
Embodiment
First photoconductive layer of the present invention is characterised in that it comprises the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se.When monovalent metal during less than 0.1 molar ppm maybe when the chalcogen except that Se during less than 0.1 molar ppm, can not suppress the sensitivity variation, the after image characteristic of photoconduction is not enough.When monovalent metal during greater than 1000 molar ppm, crystallization and/or dark current take place easily to be increased.When the chalcogen except that Se during greater than 1000 molar ppm, because fractionation etc. are difficult to repeatedly form photoconductive layer.
When forming the film that wherein contains monovalent metal and the chalcogen except that Se, for example, will with it selenium alloy of monovalent metal and the reaction of the chalcogen except that Se can be deposited onboard with known depositing device.
Second photoconductive layer of the present invention is characterised in that it comprises the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and 0.1～4000 molar ppm V group element.When monovalent metal during less than 0.1 molar ppm or, can not suppress crystallization fully when V chalcogen during less than 0.1 mole of pp.When monovalent metal was not less than 1000 molar ppm, even contain V group element, crystallization and/or dark current also take place easily to be increased.When V group element is not less than 4000 molar ppm, because fractionation etc. are difficult to repeatedly form photoconductive layer.
In order to form the film that wherein contains monovalent metal and V chalcogen, for example, can will with it selenium alloy of monovalent metal and V group element reaction be deposited onboard with known depositing device.
Direct converting system and indirect conversion system are arranged in the radiation image taking panel.First and second photoconductive layers of the present invention can be applied in direct converting system and the indirect conversion system.In direct converting system, directly convert radioactive ray to electric charge, store charge is in the indirect conversion system, with for example CsI:Tl or Gd
2O
2Scintillators such as S:Tb once convert radioactive ray to light, convert light to electric charge with the a-Si photodiode, store charge.Radioactive ray for example can be gamma-rays and alpha ray and X ray.
First and second photoconductive layers of the present invention can be applied to so-called smooth reading system (in described smooth reading system, form and the projection of response radioactive ray produces the radiation image sensor reading images of electric charge) and reading system with the based semiconductor material (in described reading system, store response radioactive ray projection generation electric charge and by a pixel of a pixel for example open and close that TFT transistor electric transducers such as (thin-film transistors) reads the electric charge of storage) in.Below back kind system is called " TFT system ".
At first describe with reference to Fig. 1, Fig. 1 is the profile of radiation image taking panel of using the light reading system of first and second photoconductive layers of the present invention.
Electric charge (the sub-image electric charge that radiation image taking panel 10 comprises record radioactive ray L1 (back descriptions) permeable first conducting shell 1, when exposure the record radioactive ray L1 that passes first conducting shell 1 is shown conductive record radioactive ray conducting shell 2, is with for first conducting shell 1; Negative electrical charge for example) plays insulating material effect and substantially for the opposite polarity electric charge (transfer charge of polarity and sub-image electric charge; Positive charge for example) play substantially the charge transfer layer 3 of electric conducting material effect, when exposure, show and conductively read photoconductive layer 4 and for permeable second conducting shell 5 of electromagnetic wave L2 to reading light L2 (back description).
Can between first conducting shell 1 and record radioactive ray conducting shell 2, inject the barrier layer by the configuration electronics.Inject the barrier layer as electronics, use antimony trisulfide or N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-[1,1 '-diphenyl]-4,4-diamines (TPD).Can and read injection barrier layer, configuration hole between the photoconductive layer 4 at second conducting shell 5.Inject the barrier layer as the hole, use cerium oxide, antimony trisulfide or zinc sulphide.
As first and second conducting shells 1 and 5, preferably comprise those layers of the conductive material that is coated on equably on the transparency glass plate (for example nesa coating (nesa film)).More specifically, preferably comprise polycrystalline ITO (In
2O
3: Sn), amorphous ITO (In
2O
3: Sn), amorphous IZO (In
2O
2: Zn), ATO (SnO
2: Sb), FTO (SnO
2: F), AZO (ZnO:Al), GZO (ZnO:Ga), the film of gold, silver, platinum, aluminium, indium etc., and those of the coated film of the dispersion liquid of the noble metal of 10～1000nm (platinum, gold, silver).
The mobility of the negative electrical charge of first conducting shell 1 and and the mobility of the opposite polarity positive charge of first conducting shell 1 between difference big more, charge transfer layer 3 is good more, as charge transfer layer 3, suitable has: organic compound; For example poly N-vinyl carbazole (PVK), N, N '-diphenyl-N, N '-two (3-aminomethyl phenyl)-[1,1 '-diphenyl]-4,4-diamines (TPD) or discotheque liquid crystal; Polymer＜Merlon of TPD, polystyrene, PVK, polyvinyl alcohol〉dispersion liquid; As
2Se
3Sb
2S
3Silicone oil; Semi-conducting material, the a-Se of 10～200ppm Cl that for example mixes; Merlon; Deng.Especially, because organic compound (PVK, TPD, discotheque liquid crystal etc.) is insensitive to light, so preferably have organic compounds (PVK, TPD, discotheque liquid crystal etc.), simultaneously, because described organic compound generally has little dielectric constant, so charge transfer layer 3 and read photoconductive layer 4 and have little capacity, thereby the signal can increase reading images the time takes out efficient.
As reading photoconductive layer 4, contain wherein that at least a light-guide material as major constituent is suitable in the following material.That is, a-Se, Se-Te, Se-As-Te, the As of the a-Se of a-Se, 10～200ppm Cl that mixes, 5～200ppm As that mixes
2Se
3, metal-free phthalocyanine, metal phthalocyanine, MgPc (magnesium phthalocyanine), VoPc (the phase II of vanadyl phthalocyanine), CuPc (copper phthalocyanine), Bi
12MO
20(M:Ti, Si, Ge), BiM
3O
12(M:Ti, Si, Ge), Bi
2O
3, BiMO
4(M:Nb, Ta, V), Bi
24B
2O
39, ZnO, ZnS, ZnSe, ZnTe, MNbO
3(M:Li, Na, K), PbO, HgI
2, PbI
2, CdS, CdSe, CdTe, BiI
3Deng.In addition, can suitably adopt the selenium alloy of the V group element of the monovalent metal that wherein contains the 0.1-1000 molar ppm and 0.1-4000 molar ppm.
As record radioactive ray conducting shell 2, use photoconductive layer of the present invention.That is to say that photoconductive layer of the present invention is record radioactive ray conducting shells.In the situation of first photoconductive layer of the present invention, preferred monovalent metal adds with the form of chalcogenide.When monovalent metal is Na, with Na
2Se, Na
2S and Na
2The form of Te adds Na.Na can Na
2SeO
3, NaOH and NaCl form add.Preferred S and Te add each as simple form (simplex).In the situation of second photoconductive layer of the present invention, preferred monovalent metal adds with the form of chalcogenide.When monovalent metal is Na, although can be with Na
2S and Na
2The form of Te adds, but preferably with Na
2The form of Se adds Na.Although preferred As is with As
2Se
3Or the form of the selenium of simple form, doping As adds, Sb is with Sb
2Se
3Or the form of simple form adds and Bi with Bi
2Se
3Or the adding of the form of simple form, but they can add with the form of sulfide or tellurides.
Describe briefly below and make the system that uses up in order to read electrostatic latent image.Fig. 2 represents to use the record/reading system (wherein electrostatic latent image register system and electrostatic latent image reading system are integrated) of radiation image taking panel 10.Record/reading system comprises radiation image taking panel 10, record radioactive ray grenade instrumentation 90, power supply 50, current sensing means 70, reads exposure device 92 and a pair of jockey S1 and S2.The electrostatic latent image recording section comprises radiation image taking panel 10, power supply 50, record radioactive ray grenade instrumentation 90 and jockey S1, and the electrostatic latent image reading section comprises radiation image taking panel 10, current sensing means 70 and jockey S2.
First conducting shell 1 of radiation image taking panel 10 utilizes jockey S1 to be connected on the negative terminal of power supply 50 and is connected to the end of jockey S2.The other end of jockey S2 can move in the 3rd position that neither connects current sensing means 70 also earth-free but the primary importance of opening, the second place that is connected to current sensing means 70 and ground connection.Second conducting shell 5 of radiation image taking panel 10 and the positive terminal of power supply 50 be ground connection all.Current sensing means 70 comprises detecting amplifier 70a (operational amplifier) and feedback resistor 70b, forms so-called current-voltage conversion circuit.
Second conducting shell 5 for example has, and Japanese unexamined patent discloses disclosed structure in 2001-337171 and the 2001-160922 communique.
On the upper surface of first conducting shell 1, place object 9, object 9 has permeable permeable part 9a of radioactive ray L1 and the impermeable radioactive ray cut-off parts of radioactive ray L1 9b.Record radioactive ray grenade instrumentation 90 projects radioactive ray L1 on the object 9 equably, reads exposure device 92 simultaneously and reads light L2 with scanning direction shown in the arrow among Fig. 2, and reading light L2 for example is by LED, organic EL or inorganic EL emitted laser bundle or light.Read light L2 and preferably have the linear convergence shape.
The electrostatic latent image of describing in record/reading system with reference to the charge model shown in Fig. 3 A～3D forms program.When the other end of described jockey S2 is placed on the both earth-free also primary importance that does not connect current sensing means 70 but open and opens jockey S1, between first and second conducting shells 1 and 5, apply direct voltage Ed by power supply 50, first conducting shell 1 is charged to negative electrical charge, second conducting shell 5 is charged to positive charge (Fig. 3 A) simultaneously, thereby sets up parallel electric field between first and second conducting shells 1 and 5 of radiation image taking panel 10.
Then, radioactive ray L1 throws to object 9 equably from record radioactive ray grenade instrumentation 90.Radioactive ray L1 is by the permeable part 9a and first conducting shell 1 of object 9.When being exposed to the radioactive ray L1 that passes through, record radioactive ray conducting shell 2 shows conductibility gradually.This can be understood as since record radioactive ray conducting shell 2 serve as variable resistance that resistance can change with the amount of radioactive ray and since resistance depend on that radioactive ray L1 produces comprise the charged right of electronics (negative electrical charge) and hole (positive charge), along with the amount reduction of the radioactive ray L1 that passes through object 9, record radioactive ray conducting shell 2 shows bigger resistance.Negative electrical charge that (Fig. 3 B) produced by radioactive ray L1 and positive charge in Fig. 3 A～3D and Fig. 4 A～4D with zone circle-or+represent.
The positive charge that produces in the record radioactive ray conducting shell 2 is being shifted to first conducting shell 1 with writing down radioactive ray conducting shell 2 high speeds, and the negative electrical charge of being with first conducting shell 1 reconfigures, and disappears.The negative electrical charge that produces in (Fig. 3 C and 3D) record radioactive ray conducting shell 2 is shifted to charge transfer layer 3 in record radioactive ray conducting shell 2.Because the electric charge that 3 pairs of charge transfer layers and first conducting shell 1 are with is (in this special scheme, being negative electrical charge) electric charge that polarity is identical plays the insulating material effect substantially, the interface of negative electrical charge between record radioactive ray conducting shell 2 and charge transfer layer 3 of moving in record radioactive ray conducting shell 2 stops, and assembles thereon.The quantity of electric charge that (Fig. 3 C and 3D) assembles promptly passes through the amount decision of the radioactive ray L1 of object 9 by the amount of the negative electrical charge that produces in the record radioactive ray conducting shell 2.
Because radioactive ray L1 does not pass through the radioactive ray cut-off parts 9b of object 9, so the part of radiation image taking panel 10 under cut-off parts 9b remains unchanged.(Fig. 3 B～3D) is by being exposed to radioactive ray L1 with object 9 like this, can accumulate on the interface between record radioactive ray conducting shell 2 and the charge transfer layer 3 according to the electric charge of the image of object 9.The image of the object of being represented by the electric charge of assembling 9 is called " electrostatic latent image ".
With reference to the charge model shown in Fig. 4 A～4D described the electrostatic latent image fetch program.Open jockey S1, jockey S2 ground connection once to rearrange electric charge by first and second conducting shells 1 and 5 chargings of giving radiation image taking panel 10 in the same potential shown in Fig. 4 A, is connected on the current sensing means 70 then.
Then, when making second conducting shell 5 that reads light L2 scanning radiation image taking panel 10 with reading exposure device 92, read light L2 by second conducting shell 5, impinge upon and read on the light photoconductive layer 4, be exposed to the light photoconductive layer 4 that reads that reads light L2 and show conductibility when reading light L2 gradually being exposed to.This depends on, and reads 4 responses of light photoconductive layer the exposure of reading light L2 is produced negative electrical charge and positive charge, is similar to, and radioactive ray photoconductive layer 2 is owing to the exposure generation negative electrical charge and the positive charge that respond radioactive ray L1 show conductibility.(Fig. 4 B) is similar to logging program, by read negative electrical charge that light L2 produces and positive charge in Fig. 3 A～3D and Fig. 4 A～4D with zone circle-or+represent.
Because 3 pairs of positive charges of charge transfer layer play the conductor effect, the positive charge that produces in the photoconductive layer 4 is rapidly by charge transfer layer 3, as the charge attraction that they are assembled, the interface between radioactive ray photoconductive layer 2 and charge transfer layer 3 and the electric charge of gathering reconfigure, and disappear.Negative electrical charge that produces in (Fig. 4 C) photoconductive layer 4 and the positive charge on second conducting shell 5 reconfigure, and disappear.(Fig. 4 C) reads light L2 scan light conducting shell 4 with what have a substantial light amount.Therefore, accumulate in the gathering electric charge on the interface between radioactive ray photoconductive layer 2 and the charge transfer layer 3, promptly electrostatic latent image all disappears by charge recombination.The electric charge of assembling in the radiation image taking panel 10 disappears and means, because movement of electric charges, electric current I flows in radiation image taking panel 10, this state can be represented with equivalent electric circuit, for example shown in Fig. 4 D, wherein radiation image taking panel 10 electricity consumption source-representations, the magnitude of current of power supply depends on the amount of the electric charge of collection.
Detect the electric current that flows out radiation image taking panel 10 when reading light L2, can in turn read every part (respective pixel) and go up the quantity of electric charge of assembling, thereby read out electrostatic latent image in scanning.The effect of reading section is disclosed in Japanese unexamined patent and discloses in 2000-105297 communique etc.
The radiation image taking panel of TFT system is described below.As shown in Figure 5, the radiation image taking panel comprises the radioactive ray test section 100 and the activity matrix array board (after this will be called " AMA plate ") of mutual bonding.As shown in Figure 6, radioactive ray test section 100 broadly comprises public electrode 103, photoconductive layer 104 that produces charge carrier that applies bias voltage and the detecting electrode 107 of collecting charge carrier, each of described charge carrier all is electron-hole pair, the target radiation line that sensing will detect, above-mentioned public electrode 103, photoconductive layer 104 and detecting electrode 107 are in proper order stacked according to this from a side of radioactive ray bump radiation image taking panel.Radioactive ray test section carrier can be with layered arrangement above public electrode 103.
The structure of AMA plate 200 is described below briefly.As shown in Figure 7, in AMA plate 200, all dispose electric capacity 210 and TFT220 for each radioactive ray test section 105 corresponding to pixel.Each electric capacity 210 all has the electric capacity that conforms to the electric charge of assembling, and TFT 220 is as conversion element.In carrier 102, corresponding to each radioactive ray test section 105 bidimensional of pixel (for example be arranged in matrix, number of pixels as required, vertical direction 1000～3000, horizontal 1000～3000) in, in AMA plate 200, be arranged in the same matrix electric capacity 210 that number is identical with pixel and TFT220 bidimensional.The accumulation that photoconductive layer produces forms sub-image in electric capacity 210.In the TFT system, the sub-image that radioactive ray produce is kept by electric capacity 210.
As shown in Figure 6, electric capacity 210 and TFT 220 have ad hoc structure in AMA plate 200.Promptly; AMA plate pedestal 230 is insulators; the source electrode 220b of the connection electrode 210b of electric capacity 210 and TFT 220 and drain electrode 220c are laminated on the grounding electrode 210a of electric capacity 210; form the gate electrode 220a of TFT 220 in its surface in the mode of dielectric film 240 with electric capacity 210 surfaces, TFT 220 protected dielectric films 250 coat.In addition, the source electrode 220b of the connection electrode 210b of electric capacity 210 and TFT 220 is incorporated in the electrode, forms simultaneously.Dielectric film 240 as the dielectric film of the grid of capacitor insulating film that forms electric capacity 210 and TFT 220 for example uses plasma SiN film.Use film technique and/or fining-off technology, for example be used to prepare the technology of the substrate of LCD, preparation AMA plate 200.
The bonding of radioactive ray test section 100 and AMA plate 200 is described below.For connection electrode 210b positioned detection electrode 107 with respect to electric capacity 210, with anisotropic conductive film (ACF) hot adhesion plate 100 and 200, described anisotropic conductive film for example comprises conductive particle such as silver-colored particle therein and only have conductivity on thickness direction, be inserted in the middle of them, thereby plate 100 and 200 is mechanically integrated, and detecting electrode 107 and connection electrode 210b are electrically connected in the mode of inserting conductivity part 140.
The radiation image camera system that radioactive ray test section 100 and AMA plate 200 bond together for example in disclosing the 11st (1999)-No. 287862 communique, Japanese unexamined patent is disclosed.
The embodiment of first photoconductive layer of the present invention is shown below.
(embodiment 1～12, Comparative Examples 2～6)
High-purity selenium (6NSuper:Ohsaka Asahi Metal) adds Na
2Se, is contained in the quartz ampoule with doping Te with doping Na and amorphous tellurium, vacuumizes, and sealing makes their 500 ℃ of reactions down, makes the selenium alloy shown in the table 1.Selenium alloy is contained in the stainless steel crucible, and the deposition Se film that wherein contains Na and Te is formed on the amorphous IZO glass substrate at the thickness with 200 μ m under the following condition: 300 ℃ of crucible temperature, vacuum degree 0.0001Pa, 65 ℃ of substrate temperatures and deposition rate 1 μ m/min.Use the Se film that makes like this, prepare the device of the thick top electrode (upper electrode of gold) of 100nm with deposition process with gold.
(embodiment 13～17, Comparative Examples 7)
Except replacing with amorphous sulphur the amorphous tellurium, use with the same way as of embodiment 1 to have the selenium alloy preparation facilities of forming shown in the table 1.
(Comparative Examples 1)
Except high-purity selenium undopes Na and the Te, with the same way as preparation facilities of embodiment 1.
(mensuration of (Lag) after image that lags behind)
Project on the sample with 2 seconds X ray under the condition of 30kV (voltage) with the MO pipe 1R, under the condition identical, convert the pulse sample photoelectric current that produces to voltage, measure the X ray photo-signal with digital oscilloscope with current amplifier with the condition that applies voltage.The voltage that applies is equivalent to the electric field of 10V/ μ m.30 seconds electric current-time that mensuration obtains, the absolute value representation Lag of the common logarithm of the ratio of maximum photoelectric current when throwing with X ray with the back 15 seconds photoelectric current intensity of X ray projection end.Absolute value is big more, and after image characteristic is excellent more.
(analysis of the raw material that uses in the device)
Carry out the analysis of raw material with glow discharge mass spectrometry (glow-discharge mass spectrometry is called for short GDMS).Concentration of element is represented molar fraction with respect to each mole selenium with ppm in the selenium.The 6N of Comparative Examples high-purity (super) selenium is less than the mensuration limit value of concentration of element, and Na concentration, S concentration and Te concentration are respectively less than 0.03 molar ppm, 0.01 molar ppm and 0.03 molar ppm.
The result is illustrated in the following table 1.
Table 1
As can be understood from Table 1, because each device of embodiment 1～17 is formed by the Se alloy that wherein contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se, so the problem of the sensitivity variation of each device of embodiment 1～17 alleviates, the rate of decay aspect of X ray photoelectric current is improved.Although in the situation of the partial animations of 5 frame/seconds or the animation of 5～30 frame/seconds, when image is influenced by the signal of telecommunication of front sensing, exist image to become problem unintelligible or that disturb, but, because first photoconductive layer of the present invention has excellent after image characteristic, so even first photoconductive layer of the present invention is applied to animation, it does not allow to be subject to the signal of telecommunication influence of front sensing yet, let alone is applied to partial animation.
Although at the Comparative Examples 1 of undope monovalent metal and the chalcogen except that Se and doping monovalent metal and the chalcogen except that Se but in the few Comparative Examples 2,3 and 7 of their amount, the rate of decay of X ray photoelectric current is improved insufficiently.In embodiment 7～9 and 11, although doping monovalent metal and the chalcogen except that Se, their amount will excess, the trend that the rate of decay of X ray photoelectric current becomes relatively poor occurs.In Comparative Examples 4～6 and 11, although doping monovalent metal and the chalcogen except that Se, their amount is too big, and it is poorer that the rate of decay of X ray photoelectric current becomes significantly.
In embodiment 1～6 and 10～17, the Na content of Se alloy raw material is between 0.2～200 molar ppm, and the after image characteristic of photoconductivity can obtain bigger improvement.
(analysis of deposited film in the device)
For the concentration of element in the deposited film of the device of measuring Comparative Examples 1 and embodiment 4, prepare silicon wafer (silicone wafer) with the square glass substrate of 5cm of arranging amorphous IZO layer and comb electrode (comb electrode) on it, under the condition of Comparative Examples 1 and embodiment 4, deposit simultaneously.The on-chip whole selenium alloys of organosilicon are dissolved in the nitric acid, with the quantitative selenium amount in this solution of ICP fluorescence method, use the quantitatively amount of Na and Te in this solution of graphite mould atomic absorption spectrum and ICP-MS simultaneously respectively.Obtain the concentration of each atom with respect to selenium.At this moment,, wash twice with water removing the Na that is not added in the selenium layer in order to eliminate the influence that surperficial Na pollutes, K etc., and in icp analysis, carry out being not more than for twice the etching of 0.1nm, almost detect less than selenium this moment.Under the inorganic layer except that selenium or organic layer are set at situation on the selenium layer, by owing to the strain stress (strain stress) that produces by the change in volume that the selenium layer crystallization is caused or owing to peeling off that the differential expansion that the selenium layer quenching is produced causes, can obtain being attached on the substrate or the selenium layer that isolates.
The amount of Na and Te is respectively less than 0.001 molar ppm with less than 0.07 molar ppm, less than detecting limit value in the device of Comparative Examples 1.And the amount of Na and Te is respectively 0.01 molar ppm and 3 molar ppm in the device of embodiment 4.This fact shows that Na is difficult to be incorporated in the selenium when deposition, and the concentration of Te tends to be slightly less than the concentration of Te in the raw material in the deposited film.
Be appreciated that from above-mentioned explanation, because first photoconductive layer of the present invention comprises the Se alloy that wherein contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se, so the rate of decay of the X ray photoelectric current of first photoconductive layer of the present invention is improved, thereby because animated characteristics is excellent and the time interval of formation image can shorten, output increases and the after image characteristic of photoconductivity can be improved.
The embodiment of second photoconductive layer of the present invention is shown below.
(embodiment 1～10, Comparative Examples 2～6)
Arranged thereon to form the comb electrode on the square glass substrate of 5cm of amorphous IZO layer, used vacuum-metallize device (vacuum metallizer) under following condition, high-purity selenium (6NSuper:Ohsaka Asahi Metal) to be deposited as the thick Se film of 10 μ m: 300 ℃ of crucible temperature, vacuum degree 0.0001Pa, 65 ℃ of substrate temperatures and deposition rate 1 μ m/min.In addition, under 460 ℃ crucible temperature with As
2Se
3(6N:Huruuchi Kagaku) is with the thickness lamination of 0.2 μ m on it.In addition, high-purity selenium adds Sb
2Se
3And Na
2Se in the quartz ampoule of packing into, vacuumizes, and sealing makes them 550 ℃ of reactions down, makes the selenium alloy shown in the table 2.Changing under 55 ℃ the wide temperature, under the condition of the deposition rate of 1 μ m/min, selenium alloy is being deposited as the thick deposited film of 200 μ m.The device for preparing the thick top electrode of 600nm by sputter with gold.
(embodiment 11～20, Comparative Examples 7-11)
Remove and use As
2Se
3Replace Sb
2Se
3Use selenium alloy preparation facilities with the same way as of embodiment 1 outward, with composition shown in the table 2.
(Comparative Examples 1)
Except that high-purity selenium undopes Na and the Te, with the same way as preparation facilities of embodiment 1.
(amount and the image deflects of assembling electric charge)
Use Japanese unexamined patent to disclose the amount that disclosed image read system mensuration is assembled electric charge in the 2004-147255 communique.Measure image deflects in the following manner.Promptly, do not use radioactive ray with the two dimensional image output signal, utilize same reading system that light is projected on the object, counting is not less than the point of 10 μ m, measure in the same manner after two weeks at 40 ℃ of following subsequent dryings simultaneously and count, calculate the ratio of the image deflects between these time front and back thus.
(analysis of used raw material in the device)
(GDMS) carries out the analysis of raw material with glow discharge spectrometry.Concentration of element is represented the molar fraction of each mole selenium in the selenium with ppm.The 6N super selenium of Comparative Examples 1 is less than the mensuration limit value of concentration of element, and Na concentration, S concentration and Te concentration are respectively less than 0.03 molar ppm, 0.06 molar ppm and 1 molar ppm.
The result is illustrated in the following table 2.Assembling the amount and the image deflects ratio of electric charge all represents with the relative value with respect to Comparative Examples.
Table 2
As can be understood from Table 2, because each device of embodiment 1～20 is to be formed as raw material by the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and 0.1～40 molar ppm V group element, so compare with the device of the Comparative Examples 1 that does not have monovalent metal and V group element in the table 2, the amount of their gathering electric charge is bigger, can suppress image deflects increase in time more.In addition, the Comparative Examples 2 that is lower than 0.1 molar ppm with monovalent metal content is compared, the amount of the gathering electric charge of each device of embodiment 1～17 is bigger, compares with 7 device less than the Comparative Examples 3,4 of 0.1 molar ppm with V group element content, can suppress image deflects increase in time significantly.Find from Comparative Examples 5 and 6, when Na content is not less than 1000 molar ppm, even the Sb that adds in the V group element can not suppress image deflects increase in time.
Embodiment 7 and 9 comparison shows that, when V group element content was too high, although can suppress image deflects increase in time, the amount of assembling electric charge reduced.
The device that is formed by the selenium alloy that wherein contains the As that is not more than 4000 molar ppm has the excellent gathering quantity of electric charge, and the problem that does not exist image deflects to increase in time.
(analysis of deposited film in the device)
For the concentration of element in the deposited film of the device of measuring Comparative Examples 1 and embodiment 2, silicon wafer prepares with the square glass substrate of 5cm of arranging amorphous IZO layer and comb electrode on it, deposits simultaneously under the condition of Comparative Examples 1 and embodiment 6.The on-chip whole selenium alloy films of organosilicon are dissolved in the nitric acid, with the quantitative selenium amount in this solution of ICP fluorescence method, use the quantitatively amount of Sb and As in this solution of graphite mould atomic absorption spectrum and ICP-MS simultaneously respectively.Obtain the concentration of each atom with respect to selenium.At this moment,, wash twice with water removing the Na that is not added in the selenium layer in order to eliminate the influence that surperficial Na pollutes, K etc., and in icp analysis, carry out being not more than for twice the etching of 0.1nm, almost detect less than selenium this moment.
Under the inorganic layer except that selenium or organic layer are set at situation on the selenium layer, by owing to the strain stress (strain stress) that produces by the change in volume that the selenium layer crystallization is caused or owing to peeling off that the differential expansion that the selenium layer quenching is produced causes, can obtain being attached on the substrate or the selenium layer that isolates.
The amount of Na and Sb is respectively less than 0.02 molar ppm and 0.07 molar ppm, less than detecting limit value in the device of Comparative Examples 1.And the amount of Na and Sb is respectively 0.03 molar ppm and 0.2 molar ppm in the device of embodiment 2.This fact shows that Na is difficult to be incorporated in the selenium when deposition, and the concentration of Sb tends to be slightly less than the concentration of Sb in raw materials in the deposited film.Na concentration is 0.03 molar ppm in embodiment 14 and 20 the device, and As concentration is respectively 45 molar ppm and 980 molar ppm in the device of embodiment 14 and 20.This fact shows that concentration is tended to along with As concentration increases and reduces from the concentration raw material in the deposited film.
Be appreciated that from above-mentioned explanation, in second photoconductive layer of the present invention, because second photoconductive layer of the present invention comprises the selenium alloy that wherein contains 0.1～1000 molar ppm monovalent metal and 0.1～4000 molar ppm V group element, so can prevent local-crystalized, improve carrier mobility, thereby can suppress image deflects increase in time.
Claims (16)
1. a photoconductive layer that forms the radiation image taking panel is characterized in that described photoconductive layer is formed by selenium alloy, and described selenium alloy contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se therein.
2. photoconductive layer as claimed in claim 1, wherein said monovalent metal are Na, and selenium alloy contains the Na of 0.2～200 molar ppm therein.
3. photoconductive layer as claimed in claim 2, wherein chalcogen is Te, selenium alloy contains the Te of 0.1～400 molar ppm therein.
4. photoconductive layer as claimed in claim 1, wherein chalcogen is Te, selenium alloy contains the Te of 0.1～400 molar ppm therein.
5. a photoconductive layer that forms the radiation image taking panel is characterized in that described photoconductive layer comprises selenium alloy, and described selenium alloy contains 0.001～10 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se therein.
6. a radiation image taking panel is characterized in that, described radiation image taking panel comprises the photoconductive layer of being made by selenium alloy, and described selenium alloy contains 0.001～10 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se therein.
7. a radiation image taking panel is characterized in that, described radiation image taking panel comprises the photoconductive layer that contains selenium alloy, and described selenium alloy contains 0.1～1000 molar ppm monovalent metal and the chalcogen of 0.1～1000 molar ppm except that Se therein.
8. a photoconductive layer that forms the radiation image taking panel is characterized in that described photoconductive layer is formed by selenium alloy, and described selenium alloy contains 0.1～1000 molar ppm monovalent metal and 0.1～4000 molar ppm V group element therein.
9. photoconductive layer as claimed in claim 8, wherein monovalent metal is Na, selenium alloy contains the Na of 0.2～300 molar ppm therein.
10. photoconductive layer as claimed in claim 8, wherein V group element is Sb, selenium alloy contains the Sb of 0.15～20 molar ppm therein.
11. photoconductive layer as claimed in claim 9, wherein V group element is Sb, and selenium alloy contains the Sb of 0.15～20 molar ppm therein.
12. photoconductive layer as claimed in claim 8, wherein V group element is As, and selenium alloy contains the As of 1.5～4000 molar ppm therein.
13. photoconductive layer as claimed in claim 9, wherein V group element is As, and selenium alloy contains the As of 1.5～4000 molar ppm therein.
14. a photoconductive layer, it comprises selenium alloy, and wherein said selenium alloy contains the V group element of 0.001～10 molar ppm monovalent metal and 0.1-2000 molar ppm therein.
15. a radiation image taking panel is characterized in that described radiation image taking panel comprises the photoconductive layer of being made by selenium alloy, described selenium alloy contains 0.1～1000 molar ppm monovalent metal and 0.1～2000 molar ppm V group element therein.
16. a radiation image taking panel is characterized in that described radiation image taking panel is formed by photoconductive layer, described photoconductive layer is made by selenium alloy, and described selenium alloy contains 0.1～1000 molar ppm monovalent metal and 0.1～4000 molar ppm V group element therein.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005-318840 | 2005-11-01 | ||
| JP2005318840 | 2005-11-01 | ||
| JP2005-318839 | 2005-11-01 | ||
| JP2005318839 | 2005-11-01 | ||
| JP2005318840 | 2005-11-01 | ||
| JP2005318839 | 2005-11-01 |
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| CN1959997A CN1959997A (en) | 2007-05-09 |
| CN1959997B true CN1959997B (en) | 2010-12-01 |
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| CN2006101432525A Active CN1959997B (en) | 2005-11-01 | 2006-11-01 | Photoconductive layer forming radiation image taking panel and radiation image taking panel |
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| Country | Link |
|---|---|
| US (1) | US20070099116A1 (en) |
| EP (1) | EP1780800A3 (en) |
| CN (1) | CN1959997B (en) |
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| JP5070130B2 (en) * | 2008-05-26 | 2012-11-07 | 富士フイルム株式会社 | Radiation detector |
| JP6132283B2 (en) * | 2013-05-17 | 2017-05-24 | Ｎｌｔテクノロジー株式会社 | Amplifier circuit and image sensor using the amplifier circuit |
| CN104183726A (en) * | 2013-05-21 | 2014-12-03 | 海洋王照明科技股份有限公司 | Organic light emission diode and preparation method thereof |
| KR102563942B1 (en) | 2016-11-30 | 2023-08-04 | 더 리서치 파운데이션 포 더 스테이트 유니버시티 오브 뉴욕 | Hybrid Active Matrix Flat Panel Detector System and Method |
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| EP0301903A2 (en) * | 1987-07-31 | 1989-02-01 | Canon Kabushiki Kaisha | Functional ZnSe1-xTeX: H deposited film |
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| US3685989A (en) * | 1970-12-18 | 1972-08-22 | Xerox Corp | Ambipolar photoreceptor and method of imaging |
| US4370399A (en) * | 1981-03-23 | 1983-01-25 | A. B. Dick Company | Equisensitive ambipolar indium doped selenium containing electrophotographic materials, plates and method |
| US4548800A (en) * | 1982-08-02 | 1985-10-22 | Xerox Corporation | Process for selenium purification |
| US4582772A (en) * | 1983-02-15 | 1986-04-15 | Xerox Corporation | Layered photoconductive imaging devices |
| US4626486A (en) * | 1983-04-08 | 1986-12-02 | Ricoh Co., Ltd. | Electrophotographic element comprising alloy of selenium and tellurium doped with chlorine and oxygen |
| US4467023A (en) * | 1983-08-15 | 1984-08-21 | Xerox Corporation | Layered photoresponsive device containing hole injecting ground electrode |
| US4484945A (en) * | 1984-03-12 | 1984-11-27 | Xerox Corporation | Process for preparation of chalcogenide alloys by solution coreduction of a mixture of oxides |
| US4888521A (en) * | 1986-07-04 | 1989-12-19 | Hitachi Ltd. | Photoconductive device and method of operating the same |
| US4770965A (en) * | 1986-12-23 | 1988-09-13 | Xerox Corporation | Selenium alloy imaging member |
| US4863508A (en) * | 1987-10-01 | 1989-09-05 | Xerox Corporation | Process for the preparation of chalcogenide alloys by the solution oxidation of alkaline selenium and alkaline tellurium compounds |
| ES2073406T3 (en) * | 1987-11-20 | 1995-08-16 | Canon Kk | PHOTOVOLTAIC ELEMENT WITH PIN UNION WITH A SEMICONDUCTIVE LAYER OF TYPE PO OF TYPE N THAT INCLUDES A NON-GLASS MATERIAL SINGLE CONTAINING ZN, SE, TE, H IN A QUANTITY OF 1 TO 4 ATOMIC% AND A CONTAMINANT AND A SEMI-CONDUCTIVE LAYER TYPE I UNDERSTANDING A MATERIAL |
| US4859411A (en) * | 1988-04-08 | 1989-08-22 | Xerox Corporation | Control of selenium alloy fractionation |
| US5002734A (en) * | 1989-01-31 | 1991-03-26 | Xerox Corporation | Processes for preparing chalcogenide alloys |
| DE4011267C2 (en) * | 1989-04-12 | 1995-03-23 | Fuji Electric Co Ltd | Electrophotographic recording material |
| CA2184667C (en) * | 1996-09-03 | 2000-06-20 | Bradley Trent Polischuk | Multilayer plate for x-ray imaging and method of producing same |
| US6704133B2 (en) * | 1998-03-18 | 2004-03-09 | E-Ink Corporation | Electro-optic display overlays and systems for addressing such displays |
| EP1136888B1 (en) * | 2000-03-22 | 2012-01-18 | FUJIFILM Corporation | Image recording medium and method of manufacturing an image recording medium |
| JP2001284628A (en) * | 2000-03-29 | 2001-10-12 | Shindengen Electric Mfg Co Ltd | X-ray detector |
| JP4188619B2 (en) * | 2002-04-23 | 2008-11-26 | 株式会社島津製作所 | X-ray detector |
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- 2006-10-31 EP EP06022742A patent/EP1780800A3/en not_active Ceased
- 2006-11-01 CN CN2006101432525A patent/CN1959997B/en active Active
- 2006-11-01 US US11/590,780 patent/US20070099116A1/en not_active Abandoned
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0301903A2 (en) * | 1987-07-31 | 1989-02-01 | Canon Kabushiki Kaisha | Functional ZnSe1-xTeX: H deposited film |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1780800A3 (en) | 2007-07-11 |
| CN1959997A (en) | 2007-05-09 |
| EP1780800A2 (en) | 2007-05-02 |
| US20070099116A1 (en) | 2007-05-03 |
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